Stereocontrolled alkylation of unsaturated compounds with alkoxytitanacyclopropane reagents.
Interaction of titanium(IV) isopropoxide with ethylmagnesium bromide and its higher homologs leads to the generation of alkoxytitanacyclopropane species, which are able to act in the reactions with unsaturated compounds as 1,2-dicarbanionic alkylating agents. The present review is focused on the processes of intermolecular regio- and stereoselective alkylation of carboxylic esters and allylic alcohol derivatives with alkoxytitanacyclopropane reagents. The oxophilicity of the titanium atom and its tendency to form sterically crowded ate complexes are probably the main factors providing a high level of selectivity of these transformations.
Kulinkovich
Oleg
O
Department of Organic Chemistry, Belarusian State University, Nezavisimosti Ave. 4, 220030, Minsk, Belarus. kulinkovich@bsu.by
Isakov
Vladimir
V
Kananovich
Dzmitry
D
D000478:Alkylation; D002264:Carboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D003521:Cyclopropanes / Q000737:chemistry*; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D020005:Propanols / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D014025:Titanium / Q000737:chemistry*
D002264:Carboxylic Acids; D003521:Cyclopropanes; D004952:Esters; D009942:Organometallic Compounds; D020005:Propanols; C006463:allyl alcohol; D014025:Titanium